Process for breaking emulsions of the oil-in-water class



3,009,884 PROCESS FOR BREAKING EMULSION S OF THE OIL-IN-WATER CLASS Louis T. Monson, La Puente, and Fred W. Jenkins, Los

Angeles, Calif., assignors to Petrolite Corporation, Los

Angeles, Calif., a corporation of Delaware No Drawing. Filed July 29, 1957, Ser. No. 674,606

. 11 Claims. (Cl. 252-341) This invention relates to a process for resolving or separating emulsions of the oil-in-Water class, by subjecting the emulsion to the action of certain chemical reagents.

Emulsions of the oiI-in-water class comprise organic oily materials, which, although immiscible with water or aqueous or non-oily media, are distributed or dispersed as small drops throughout a continuous body of non-oily medium. The proportionof dispersed oily material is in many and possibly most cases a minor one.

Oil-field emulsions containing small proportions of crude petroleum oil relatively stably dispersed in Water or brine are representative oil-in-Water emulsions. Other oil-in-water emulsions include: certain oil-refinery emulsions, in which a petroleum distillate occurs as a disper- 'sion in-water; stem cylinder emulsions, in which traces of lubricating oil are fund dispersed in condensed steam from steam engines and steam pumps; wax-hexane-water emulsions, encountered in dewaxing operations in oil refining; butadiene tar-in-water emulsions, in the manufacture of butadiene from heavy naphtha by cracking in gas generators, and occurring particularly in the Wash box waters of such systems; emulsions of flux oil in steam condensate produced in the catalytic dehydrogenation of butylene to produce butadiene; styrene-in-water emulsions, in synthetic rubber plants; synthetic latex-in-water emulsions, in plants producing co-polymer butadiene-styrene or GRS synthetic rubber; oil-in-water emulsions occurring in the cooling Water systems of gasoline absorption plants; pipe press emulsions from steam-actuated presses in clay pipe manufacture; emulsions of petroleum residues-in-diethylene glycol, in the dehydration of natural gas.

In other industries and arts, emulsions of oily materials in water or other non-oily media are encountered, for example, in sewage disposal operations, synthetic resin emulsion paint formulation, milk and mayonnaise processing, marine ballast water disposal, and furniture polish formulation. In cleaning the equipment used in processing such products, diluted oil-in-water emulsions are inadvertently, incidentally, or accidentally produced. The disposal of aqueous wastes is, in general, hampered by the presence of oil-in-water emulsions.

Essential oils comprise non-saponifiable materials like terpenes, lactones, and alcohols. They also contain saponifiable esters or mixtures of saponifiable and nonsaponifia-ble materials. Steam distillation and other production procedures sometimes cause oil-in-water emulsions to be produced, from which the valuable essential oils are difiicultly recoverable.

In all such examples, a non-aqueous or oily material is emulsified in an aqueous or non-oily material with which it is naturally immiscible. The term oil is used herein to cover broadly the water-immiscible materials present as dispersed particles in such systems. The non-oily phase obviously includes diethylene glycol, aqueous solutions, and other non-oily media in addition to water itself.

The foregoing examples illustrate the fact that, within the broad. genus of oil-in water emulsions, there are at least three important subgenera. In these, the dispersed oilymaterial is respectively non-saponifiable, saponifiable, and a mixture of non-saponifiable and saponifiable materials. Among the most important emulsions of nonsaponifiable material in water are petroleum oil-in-water 3,009,884 Patented Nov. 21, 1961 ice emulsions. Saponifiable oil-in-Water emulsions have dispersed phases comprising, for example, saponifiable oils and fats and fatty acids, and other saponifiable oily or fatty esters and the organic components of such esters to the extent such components are immiscible with aqueous media. Emulsions produced from certain blended lubricating compositions containing both mineral and fatty oil ingredients are examples of the third sub-genus.

Oil-in-water emulsions contain widely different proportions of dispersed phase. Where the emulsion is a waste product resulting from the flushing with Water of manufacturing areas or equipment, the oil content may be only a few parts per million. Resin emulsion paints, as produced, contain a major proportion of dispersed phase. Naturally-occurring oil-field emulsions of the oilin-Water class carry crude oil in proportions varying from a few parts per million to about 20%, or even higher in rare cases.

The present invention is concerned with the resolution of those emulsions of the oil-in-water class which contain a minor proportion of dispersed phase, ranging from about 20% down to a few parts per million. Emulsions containing more than about 20% of dispersed phase are commonly of such stability as to be less responsive to the presently disclosed reagents, possibly because of the appreciable content of emulsifying agent present in such systems, whether intentionally incorporated for the purpose of stabilizing them, or not.

Although the present invention relates to emulsions containing as much as about 20% dispersed oily material,

many if not most of them contain appreciably less than this proportion of dispersed phase. In fact, most of the emulsions encountered in the development of this invention have contained about 1% or less of dispersed phase. It is to such oil-in-water emulsions having dispersed phase volumes of the order of 1% or less to which the present process is particularly directed. This does not mean that any sharp line of demarcation exists, and that, for example, an emulsion containing 1.0% of dispersed phase will respond to the process, Whereas one containing 1.1% of the same dispersed phase will remain unaffected; but that, in general, dispersed phase proportions of the order of 1% or less appear most favorable for application of the present process.

In emulsions having high proportions of dispersed phase, appreciable amounts of some emulsifying agent are probably present, to account for their stability. In the case of more dilute emulsions, containing 1% or less of dispersed phase, there may be difficulty in accounting for their stability on the basis of the presence of an emulsifying agent in the conventional sense. For example, steam condensate frequently contains very small proportions of refined petroleum lubricating oil in extremely stable dispersion; yet neither the steam condensate nor the refined hydrocarbon oil Would appear to contain anything suitable to stabilize the emulsion. In such cases, emulsion stability must probably be predicated on some basis other than the presence of an emulsifying agent.

The present process, as stated above, appears to be effective in resolving emulsions containing up to about 20% of dispersed phase. It is particularly elfective on emulsions containing not more than 1% of dispersed phase, which emulsions are the most important, in View of their common occurrence.

The present process is not believed to depend for its effectiveness on the application of any simple laws, be-

cause it has a high level of effectiveness when used toresolve emulsions of widely difierent composition, e;g., crude or refined petroleum in Water or diethylene glycol, as well as emulsions of oily materials like animal or vegetable oils or synthetic oily materials in water.

Some emulsions are byproducts of manufacturing procedures, in which the composition of the emulsion and its ingredients is known. In many instances, however, the emulsions to be resolved are either naturally-occurring or are accidentally or unintentionally produced; or in any event they do not result from a deliberate or premeditated emulsification procedure. In numerous instances, the emulsifying agent is unknown; and as a matter of fact an emulsifying agent, in the conventional sense, may be felt to be absent. It is obviously very diflicult or even impossible to recommend a resolution procedure for the treatment of such latter emulsions, on the basis of theoretical knowledge. Many of the most important applications of the present process are concerned with the resolution of emulsions which are either naturally-occurring or are accidentally, unintentionally, or unavoidably, produced. Such emulsions are commonly of the most dilute type, containing about 1% or less of dispersed phase, although concentrations up to about 20% are herein included, as stated above.

The process which constitutes the present invention consists in subjecting an emulsion of the oil-in-Water class to the action of a reagent or demulsifier of the kind subsequently described, thereby causing the oil particles in the emulsion to coalesce sufliciently to rise to the surface of the non-oily layer (or settle to the bottom, if the oil density is greater), when the mixture is allowed to stand in the quiescent state after treatment with the reagent or demulsifier.

The present application is a continuation-in-part of our co-pending application, Serial No. 643,542, filed March 4, 1957, now US. Patent 2,914,484, which latter application is concerned with a process for breaking an emulsion comprising an oil dispersed in a non-oily continuous phase, in which the dispersed phase is not greater than about 20%, characterized by subjecting the emulsion to the action of a reagent which includes a high-molal surfactant which is an oxyalkylated derivative of a 2,4,6- C -to-C -hydrocarbon-substituted monocyclic phenol c to-C -aldehyde resin, the molecular weight of the oxyalkylated derivative being within the range of about 1,000 to about 10,000. The reagents of the present application represent a sub-genus of the broad class of reagents disclosed in said co-pending application.

The reagent employed as the demulsifier in any application of our present process includes a high-molal non-ionic surfactant, which surfactant is a water-dispersible oxyalkylated derivative of an oxyalkylation-susceptible starting material. More particularly, our reagents may be referred to as crypto-cationic, as explained below.

There are three principal types or classes of surfactants: anionic, cationic, and non-ionic. In the anionic class, the molecule bears an appreciable negative charge, suflicient to cause it to migrate to the anode when its solution is exposed to direct current. Similarly, cationic surfactants bear appreciable positive charges; and their molecules tend to migrate to the cathode when their solutions are exposed to direct current. Non-ionic surfactants do not possess appreciable electric charges of either sign. However, they have the properties of surfactants generally: they adsorb positively at interfaces; they lower the surface tension of water; they ordinarily produce some foaming when their dilute aqueous solutions are agitated, etc. The present reagents are non-ionic in' character.

A crypto-cationic surfactant is one which, although it may. possessstructural characteristics or properties common to cationic compounds, possesses them only in such small or submerged degree that they are not an obvious characteristic of the finished surfactant. For example, one'may start with a basic amino compound, and introduce a large multiplicity of oxyalkylene groups by an oxyalkylation reaction, for example, by extensive oxyalkylation with ethylene oxide, or propylene, oxide or both. 'Ihe finished product, because it includes, a very large proportion of polyoxyalkylene groups, beesan atom of either oxygen, nitrogen or sulfur.

glycide, or a carbonate of such an alkylene oxide.

sentially non-ionic in character. Such amino based surfactant is an example of our crypto-cationic non-ionic surfactants.

It should be noted that, unlike the foregoing example wherein the polar nature of the starting material is responsible for the designation of the finished surfactant as crypto-cationic, the polar group may be introduced intermediate the preparation of the finished surfactant from a non-ionic starting material; or it may be introduced after the oxyalkylation reaction has been completed,

For example, one may start with a non-ionic starting material; introduce an appreciable proportion of alkylene oxide residues; then introduce one or a few moles of an alkylene imine, such as ethylene imine; and then, if desired, continue the oxyalkylation. The finished highmolal surfactant, so prepared, acts as a non-ionic'surfactant because the cationic properties incorporated therein by reaction with the imine are so small or so submerged as to be negligible. For example, one basic nitrogen atom will not confer noticeable cationic properties on an otherwise non-ionic compound having a molecular weight of the order of 1,000. Certainly it will not, when the molecular weight is, say, 8,00010,000.

The reagents employed by us in practising our process must be sufiiciently water-dispersible under the conditions of use as to be miscible with the external phase ofthe emulsions which are to be'resolved. All such emulsions are of the oil-imwater class; and hence they have water, some aqueous liquid, or at least some non-oily liquid as such external phase. Miscibility of the reagent with such phase, in the proportions required, is important if the reagent is to distribute itself throughout the emulsion in such manner as to resolve the latter.

Our reagents are all high-molal oxyalkylated derivatives of oxyalkylation-susceptible starting materials containing at least one labile hydrogen atom, that is, a hydrogen atom activated by the fact that it is attached to Alcohols, carboxylic acids, phenols, amines, amides, mercaptans, are all examples of oxyalkylation-susceptible starting ma- .terials; and the products prepared from them by an oxyalkylation reaction are oxyalkylated derivatives of them.

Oxyalkylation is a well-known reaction. Ordinarily, it is achieved by reacting an oxyalkylation-susceptible starting material with an alkylene oxide like ethylene oxide, propylene oxide, butylene oxide, glycide, or methyl- The free oxides are less expensive and more reactive than the carbonate forms, and hence are conventionally employed in the preparation of oxyalkylated derivatives of many oxyalkylation-susceptible starting materials. The

I oxyalkylation reaction using the alkylene oxides is a beautifully simple one to conduct, consisting merely in the introduction of the oxide into the starting material in presence of an alkaline catalyst (or, if the starting material is sufliciently basic, inabsence of catalyst). Where large proportions of oxyalkylene radicals are to be so introduced into the starting material, a catalyst is ordinarily employed. In the oxyalkylation reaction, the oxyalkylene residue, or multiples thereof, is introduced into the starting material betweenthe reactive or labile hydrogen atom and the adjoining oxygen, nitrogen or sulfur atom. The chain of oxyalkylene residues may be a very long one, including tens and even hundreds of recurrences of the bivalent alkylene oxide radical,

--AlkO- sizes (that is, polyoxyalkylene radicals QO IHPQSOdJQf l ferent numbers of alkylene oxide residues). The composition of oxyalkylated derivatives is therefore to be described in terms of their process of manufacture, as above.

All of our reagents are described as high-molal, in that they have theoretical molecular weights of from about 1,000 upward to about 10,000 or even greater. They are thereby distinguished from the large mass of surfactants. Simple soaps, the first widely-used and still the most widely-known class of surfactants, have molecular weights of the order of 300. Synthetic anionic detergents like keryl benzene sulfonates are surfactant-s; but their molecular weights are not greater than about 350- 400. Dinonylnaphthalene sulfonates have molecular weights less than 500. Cationic surfactants like cctylpyridinium bromide and benzyltniethyl-ammonium chloride have molecular weights less than about 400. In compounds of such lower molecular weights, the influence of a cationic element or group is significant; but, as explained above, when it is suppressed or submerged in a hig-h-molal oxyalkylation derivative of the present class, tits influence becomes negligible.

Among the crypto-cationic reagents of the present class are the reagents produced according to the following representative examples. The examples are of course not intended to be exclusive.

Example 1 A mixture of triethylenetetramine and tetraethylenepent'amine (40/60, by weight), 246 pounds, is charged into an autoclave. To it are added 738 pounds of aromatic petroleum solvent and 16 pounds of NaOH, the latter as an aqueous solution. The mixture is heated to distill the water of solution. Thereafter, 3,821 pounds of propylene oxide are introduced in continuous fashion, maintaining the temperature at about 125-130 C. and the maximum pressure at about 20 p.s.i.g. or less. Thereafter, without removing the mass from the vessel, 1,743 pounds-of ethylene oxide are introduced and similarly reacted, using the same operating conditions. The product is an effective oil-in-water dernul-sifier.

Many examples of such high-molal oxyalkyl-ated polyethylenepoly'amines are described in U.S. Patents Nos. 2,792,369-7-3, all dated May 14, 1957, to Dickson. The descriptions of those Dickson patents are incorporated herein by reference.

The above Dickson patents relate to the use of such reagents as demulsifiers for water-in-oil emulsions. Although said Dickson reagents are known to be useful as petroleum demulsifiers, it should be clearly stated that their use to date has been restricted to the resolution of water-in-oilclass petroleum emulsions, only. There is no disclosure in the Dickson patents that the same class of reagents would be suitable for resolving oil-in-w-ater class emulsions of petroleum or of any other oily liquid. Furthermore, although we have used reagents of the Dickson kind for some time, to demulsify petroleum emulsions of the water-in-oil class, we have only recently discovered their applicability in our present process, for resolving oil-in-water class emulsions.

Example 2 In the manufacture of ethanolarnines, a residue accumulates in the still which is variously designated Amine Residue T, Alkanolamine SB, Residue R, by different manufactures. Although its composition is indefinite, it is an article of commerce and is available in large quantities. To 604 pounds of such residue in an autoclave, 38 pounds of NaOH are added, in the form of a 50% aqueous solution. The mass is then heated to about 145-150- C. to drive off the water of solution. The vessel is then purged with nitrogen. Propylene oxide is thereupon introduced continuously, maintaining the temperatureat about 12.5l30 C. and the maximum pressure at about 20 p.s.i.g. or less, until a total of 4,397

pounds of propylene oxide has been so reacted. The product is an efiective oil in-water demulsifier.

Example 3 Commercial triethanolamine, 149 pounds, is placed in an autoclave, the vessel is purged with nitrogen, and propylene oxide is introduced continuously, using a reaction temperature of about 125-130 C. and a maximum pressure of about 20 p.s.i.g. or less, until a total of 250 pounds of oxide have been so reacted. Then 10 pounds of NaOH are added, in the form of a 50% aqueous solution; and the water of solution is distilled. After again purging the vessel, addition of propylene oxide is continued, until an additional 2,940 pounds have been so reacted. Then, 660 pounds of ethylene oxide are added, using the same reaction conditions. The product is an effective oil-in water demulsifier.

Example 4 Ethylene diamine is available commercially as an aqueous solution. To 71 pounds of such starting mate-rial in a previously-purged autoclave, are added 2.52. pounds of propylene oxide, using atmospheric temperature and continuing the reaction until the pressure rise so induced has subsided. Thereafter, the autoclave is heated to distill the water of solution. Then, addition of propylene oxide is continued at about 125130 C. and a maximum pressure of about 20 p.s.i.g. or less, until a total of 2,900 pounds has been so reacted. Then, without removing the product from the autoclave, ethylene oxide is similarly introduced using the same operating conditions, until a total of 5,000 pounds has been so reacted. The product is an effective oil-in-water dentuisifier.

Example 5 To 279 pounds of dehydroabietylamine (known commercially as Rosin Amine D) in a previously-purged autoclave are added 250 pounds of propylene oxide, at a temperature of 125-130" C. and a maximum pressure of about 20 p.s.i.g. Then, 10 pounds of NaOH are added, as a 50% aqueous solution. The water of solution is distilled, the autoclave is again sealed, and 330* pounds of propylene oxide are similarly reacted, using the same operating conditions. Thereafter, without removing the product from the autoclave, 176 pounds of ethylene oxide are similarly reacted, using the same operating conditions. The product is an effective oil-in-water demulsifier.

Example 6 Example 5 above is repeated; but instead of using both propylene oxide and ethylene oxide, in the presence of a catalyst, 704 pounds of ethylene oxide are reacted in absence of the NaOH catalyst. The product is an effective oil-in-water demulsifier.

Esters of the foregoing cryptc-cationic reagents, prepared by reaction with a polycarboxylic reactant, are likewise frequently useful oil-in-water demulsifiers. The following examples illustrate this aspect of our present invention.

Such esters may advantageously be prepared by reacting the aforementioned oxyalkylated material with a olycarboxy acid or anhydride. Although one may use tricarboxy acids such as citric or tricarballylic to prepare our present ester reagents, it is our preference to use a dicarboxy acid or anhydride, like oxalic acid, maleic acid or anhydride, tartaric acid, citraconic acid, phthalic acid or anhydride, adipic acid, succinic acid, azelaic acid, sebacic acid, diglycol-ic acid, adduct acids of the diene or Cl-ocker type (see Clocker, US. Patents Nos. 2,188,882- and especially such adduct acids having 8 carbon atoms or less. Polycarboxy acids having more than 8 carbon atoms may be used, such as dimerized abietic acid, dimerized fatty acids obtained from. diene acids and their esters, adduc-t acids obtained from.- terpenes and either maleic or citraconic acid or their anhydrides. .One may also use adduct acids of the type prepared by reaction between maleic anhydride, citraconic anhydride, or diglycolic acid, and butadiene or cyclopentadiene. Oxalic acid tends to decompose and is not quite as satisfactory as some of the other acids in the same price range, which are both cheap and heat-resistant. Halogenated polycarboxy acids which retain the polycarboxy function are usable reactants here.

Where'the oxyalkylated starting material used in the esterification process to produce our reagents possesses only one OH group, the product may be an acidic ester containing the residues of one molecule of each kind of reactant, or a neutral ester containing the residues of one molecule of dicarboxy acid and 2 molecules of oxyalkylated derivative. Where the parent oxyalkylated derivative contains more than one OH group, it is obvious that polyesters will result on continued reaction; and that such polyesters may be either neutral or acidic, depending on the nature of their terminal groups. In turn, that is determined largely by the proportions of reactants employed.

, We prefer to use the acidic fractional esters of this kind, as demulsifiers in our process. Accordingly, we prefervthat the esters be prepared using a stoichiometric excess of the polycarboxy acid, over what would be required to produce a neutral ester.

The following examples are representative of our present ester reagents:

Example 7 Introduce 1,000 parts by weight of the product of Example 1 above into a processing vessel equipped with stirring and heating facilities, and add 100 parts by weight of maleic anhydride, in small increments and with stirring, starting the addition at about 100 C. and slowly raising the temperature to 150 C. Stir the mass at this latter temperature for about 1 hour, stopping the process at the first appearance of insoluble rubbery polymers. The reaction massshould be watched carefully for such undesirable by-products, as the rubbery mass forms quickly after it first appears. Even slightly excessive reaction conditions should therefore be avoided. Minimi-um conditions should be employed; and the whole operation conducted cautiously. The product is an effective oi-l-in-water demulsifier. I

' Example 8 Introduce 1,000 "partsby weight of the product of Example 2 above into a processing vessel equipped with stirring and heating facilities, and add 100 parts by weight of diglycolic acid, in small increments and with stirring, starting the addition at about 100 C. and slowly raising the temperatureto 175 C. Stir the mass at this latter temperature for about 2 hours, stopping the process at the first appearance of insoluble rubbery polymers. The reaction mass should be watched; carefully for such undesirable by-products, as the rubbery mass forms quickly after it first appears. Even slightly excessive reaction conditions should therefore beavoided. Minimum conditions" should be employed; and the Whole operation conducted cautiously. The product is an effective oil-in-water demulsifier.,

Example 9 Example 10 Introduce 1,000 parts by weight of the product of Ex-, ample 4 above into a processing vessel equipped with and heating facilities, and add 120 parts by weight of phthalic anhydride, in small increments and with stirring, starting the addition at about C. and slowly raising the temperature to 200 C. Stir the mass at this latter temperature for 2 hours. The product is an effective oil-in-water demulsifier.

Example 1] Introduce 1,000 parts by weight of the product of Example 5 above into a processing vessel equipped with stirring and heating facilities, and add-100 parts by weight of diglycolic acid, in small increments and with stirring, starting the addition at about 100 C. and slowly raising the temperature to C. Stir the mass at this latter temperature for about 2 hours, stopping the process at the first appearance of insoluble rubbery polymers. The reaction mass should be watched carefully for such 1111? desirable by-products, as the rubbery mass forms quickly after it first appears. Even slightly excessive reaction conditions should therefore be avoided. Minimum conditions should be employed; and the whole operation conducted cautiously. The product is an effective oil-in water demulsifier.

Example 12 of diglycolic acid, in small increments and with stirring,

starting the addition at about 100 C. and slowly raising the temperature to 150 C. Stir the mass at this latter temperature for about 1 hour, stopping the process at the first appearance of insoluble rubbery polymers. The reaction mass should be watched carefully for such undesirable by-products, as the rubbery mass forms quickly after it first appears. Even slightly excessive reaction conditions should therefore be avoided. Minimum conditions should be employed; and the whole operation conducted cautiously. The product is an effective oil-in-water demulsifier.

Where the oxyalkylated derivative used inthe esterification process possesses only one OH group, the product can be an acidic ester containing the residues of one molecule of each kind of reactant, or a neutralester containing the residues of one molecule of dicarboxy acid and 2 molecules of oxyalkylated derivative. Where the parent oxyalkylated derivative contains more than one OH group, it is obvious that poly-esters will result on continued reaction; and that such poly-esters may be either neutral or acidic, depending on the nature of their terminal groups.

In turn, that is determined largely by the proportions of reactants employed. q q

We prefer to use the acidic fractional esters of this kind, as demulsifiers in our process. Accordingly, we prefer that the esters be prepared using a stoichiomet-ric excess of the polycarboxy acid, over what would berequired to produce a neutral ester.

Our preferred reagent is'that of Example 1 above. Our demulsifier may be applied in concentrated form, or it may be diluted with a suitable solvent, Water has frequently been found to constitute, a satisfactory solvent, because of its ready availability and negligible cost; but in other cases non-aqueous solvents, such as aromatic petroleum solvent, have been employed in preparing reagents which are effective when used for the purpose of resolving oil-in-water emulsions. Because such reagents are frequently effective in proportions of the order of 10 to 50 parts per million, their solubility in the emulsion mixture may be entirely different from their apparent solubility in bulk, in water or oil. Undoubtedly, they have some solubility in both media, within the concentration range employed.

It should be pointed out that the superiority of the reagent contemplated in the present process is based upon its ability to separate the oil phase from certain oil-inwater class emulsions more advantageously and at lower cost than is possible with other reagents or other processes. In some cases, it is capable of resolving emulsions which are not economically or effectively resolvable by any other known means.

While heat is often of little value in improving results when the present process is practised, still there are instances where the application of heat is distinctly of benefit. In some instances, adjustment of the pH of the emulsion, to an experimentally determinable optimum value, will materially improve the results obtained in applying the present process.

In operating the present process to resolve an oil-in- Water emulsion, the reagent is introduced at any convenient point in the system, and it is mixed with the emulsion in any desired manner, such as by being pumped or circulated through the system or by mechanical agitation such as paddles, or by gas agitation. After mixing, the mixture of emulsion and reagent is allowed to stand quiescent until the constituent phases of the emulsion sepa rate. Settling times and optimum mixing times will, of course, vary with the nature of the emulsions and the apparatus available. The operation, in its broadest concept, is simply the introduction of the reagent into the emulsion, the mixing of the two to establish contact and promote coalescence, and, usually, the subsequent quiescent settling of the agitated mixture, to produce the aqueous and non-aqueous emulsion phases as stratified layers.

Agitation may be achieved in various ways. The piping system through which the emulsion is passed during processing may itself supply sufficient turbulence to achieve adequate mixing of reagent and emulsion. Baflled pipe may be inserted in the flow sheet to provide agitation. Other devices such as perforated-chamber mixers, excelsioror mineralor gravelor steel-shaving-packed tanks, beds of stones or gravel or minerals in open ducts or trenches may be employed beneficially to provide mixing. The introduction of a gas, such as natural gas or air, into a tank or pipe in which or through which the mixture of reagent and emulsion is standing or passing is frequently found suitable to provide desired agitation.

It has been found that the factors, reagent feed rate, agitation, and settling time are somewhat interrelated. For example, with sufficient agitation of proper intensity the settling time required can be materially shortened. On the other hand, if agitation is relatively non-procurable but extended settling time is, the process may be equally productive of satisfactory results. The reagent feed rate has an optimum range, which is sufliciently wide, however, to meet the tolerances required for the variances encountered daily in commercial operations.

Application of a suitable gas in a procedure approximating that of the froth flotation cell employed in ore beneficiation, after the present reagent has been added to the emulsion to be resolved, frequently has a favorable influence of totally unexpected magnitude. By incorporating the step of subjecting the chemicalized emulsion to the action of air in a sub-aeration type flotation cell, a clear aqueous layer is sometimes obtained in a matter of seconds, without added quiescent settling and with approximately as much reagent. Natural gas was found to be as good a gaseous medium as was air, in this operation.

It should be distinctly understood that such aeration technique, while an important adjunct to the use of the present reagent, in some cases, is not an equivalent procedure. This may be proved by subjecting an un-chernicalized emulsion to aeration for a period of minutes without detectable favorable efiect. Addition of the reagent to such aerated emulsion will produce resolution, promptly.

The details of the mechanical structures required to produce aeration suitable for the present purpose need not be given here. It is sufiicient to state that any means 10 capable of producing small gas bubbles within the body of the emulsion is acceptable for use.

The flotation principle has long been employed in the beneficia-tion of ores. Many patents in this art illustrate apparatus suitable for producing aeration of liquids. Reference is made to Taggarts Handbook of Ore Dressing, which describes a large number of such devices.

The principle of aeration has been applied to the reso lution of emulsions by Broadbridge, in U.S. Patent No. 1,505,944, and Bailey, in US. Patent No. 1,770,476. Neither of these patents discloses or suggests the present invention, as may be seen from an inspection of their contents.

Suitable aeration is sometimes obtainable by use of the principle of Elmore, US. Patent No. 826,411. In that ore beneficiation process, an ore pulp was passed through a vacuum apparatus, the application of vacuum liberating very small gas bubbles from solution in the Water of the pulp, to float the mineral. A more recent application of this same principle is found in the Dorr Vacuator.

The manner of practicing the present invention using aeration is clear from the foregoing description.

The order in which the reagent and the aeration step are applied is relatively immaterial. Sometimes it is more convenient to chemicalize the emulsion and subsequently to apply the aeration technique. In others, it may be more advantageous to produce a strongly frothing emulsion and then introduce the reagent into such aerated emulsion.

As stated previously, any desired gas can be substituted for air. Other commonly suitable gases include natural gas, nitrogen, carbon dioxide, oxygen, etc., the gas being used essentially for its levitation effect. If any gas has some deleterious effect on any component of the emulsion, it will obviously be desirable to use instead some other gas which is inert under the conditions of use.

In summary of the foregoing: We employ as demulsifiers for oil-in-water emulsions high-molal crypto-cationic surfactants, which are oxyalkylated derivatives of oxyalkylation-susceptible starting materials, or the polycarboxy acid esters of such oxyalkylated derivatives, the molecular weight of the reagents being within the range of about 1,000 to about 10,000.

Our reagents may be employed alone, or they may in some instances be advantageously employed admixed with other and compatible oil-inwater demulsifiers. Specifically, we may employ them to advantage with the reagents described in Us. Patent No. 2,470,829, dated May 24, 1949, to Monson.

Our process is commonly practised simply by introducing small proportions of our reagent into an oil-inwater class emulsion, agitating to secure distribution of the reagent and incipient coalescence, and letting the mixture stand until the oil phase separates. The proportion of reagent required will vary with the character of the emulsion to be resolved. Ordinarily, proportions of reagent required are from about $4 to about 000 000 the volume of emulsion treated; but more or less may be required.

A preferred method of practising the process to resolve a petroleum oil-in-water emulsion is as follows: Flow the oil well fluids, consisting of free oil, oil-inwater emulsion, and natural gas, through a conventional gas separator, then to a conventional steel oil-field tank, of, for example, 5,000 bbl. capacity. In this tank the oilrn-water emulsion falls to the bottom, is withdrawn, and is so separated from the free oil. The oil-in-water emul- S1011, so withdrawn, is subjected to the action of our reagent in the desired small proportion, injection of reagent into the stream of oil-inwater emulsion being accomplished by means of a conventional proportioning pump or chemical feeder. The proportion employed in any instance is determined by trial-and-error. The mixture of emulsion and reagent then flows to a pond or sump 11 wherein it remains quiescent and the prevously emulsified oil separates, rises to the surface, and is removed. The separated water, containing relatively little to substantially none of the previously emulsified oil, is thereafter discarded.

The following will illustrate the operating steps employed to resolve an emulsion of the oil-in-water class by use of a reagent of the present kind.

A natural crude petroleum oil-in-water emulsion is subjected to the action of the product of Example 1 above. The mixture of emulsion and demulsifier is agitated for 2 minutes at 130 shakes per minute, and then allowed to stand quiescent. Separation is nearly complete after 18 hours. A check or control sample of the same emulsion, processed the same way except that no reagent is added to it, is still brown-colored at' the end of this period, whereas the treated sample is clear.

Throughout the foregoing description, we have referred to oil and to water. By oil we mean an oily, non-aqueous liquid which is not soluble in or miscible with water. :By water we mean water, aqueous solutions, and any non-oily liquid which is not soluble in or miscible with oils.

We claim;

1. A process for breaking an emulsion comprising an oil dispersed in a non-oi1y continuous phase, in which the dispersed phase is not greater than about 20%, characterized by subjecting the emulsion to the action of a reagent which includes the ester of a polycarboxy acid and a high-molal, water-dispersible, essentially non-ionic, basic nitrogen atom containing surfactant which is an oxyalkylated derivative of an oxyalkylation-susceptible starting material and of an alkylene oxide having from 2 to 4 carbon atoms selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, the molecular weight of the oxyalkylated derivative being within the range of about 1,000 to about 10,000.

' 2. The process of claim 1 in which the emulsion is a petroleum oil-in-water emulsion.

3. The process of claim 2, wherein the starting material is a polyalkylenepolyamine.

4. The process of claim 2., wherein the starting material is a polyethylenepolyarnine. c

5. The process of claim 2,'Wherein the oxyalkylated derivative is a polyoxyethylated polyoxypropylated polyethylenepolyamine.

6. The process of claim 2, wherein the ester is an ester of a polycarboxy acid having notmore than 8 carbon atoms and an oxyalkylated polyalkylenepolyamine.

7. The process of claim 6, wherein the pol'ycarboxy aoid is diglycolic acid.

- 8. The process of claim 6, wherein thepolycarboxy acid is maleic anhydride.

" 9. The process of claim 6, wherein the polycarboxy acid is phthalic anhydride.

10. The process of claim 4, wherein the polyethylene-l.

polyamine is tr-ie-thylenetetramine.

11. The process of claim 3, wherein thepolyethylene:

polyamine is tetraethylenepentamine.

References Cited in the file of this'patent UNITED STATES PATENTS OTHER REFERENCES I Schweitzer: The Creaming of Rubber Latex, article in Rubber Chemistry and Technology, vol. 13,- pp. 408 to? 414. Ucon Fluids and Lubricants, pamphlet pub. 1955', 1956 by Carbide and Carbon Chemicals Co. of New York, pp..- 24 and 36. p 

1. A PROCESS FOR BREAKING AN EMULSION COMPRISING AN OIL DISPERED IN A NON-OILY CONTINUOUS PHASE, IN WHICH THE DISPERSED PHASE IS NOT GREATER THAN ABOUT 20%, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A REAGENT WHICH INCLUDES THE ESTER OF A POLYCARBOXY ACID AND A HIGH-MOLAL, WATER-DISPERSIBLE, ESSENTIALLY NON-IONIC, BASIC NITROGEN ATOM CONTAINING SURFACTANT WHICH IS AN OXYALKYLATED DERIVATIVE OF AN OXYALKYLATION-SUSCEPTIBLE STARTING MATERIAL AND OF AN ALKYLENE OXIDE HAVING FROM 2 TO 4 CARBON ATOMS SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYGLYCIDE, THE MOLECULAR WEIGHT OF THE OXYALKYLATED DERIVATES BEING WITHIN THE RANGE OF ABOUT 1,000 TO ABOUT 10,000. 